The invention relates to a zirconium based material and more particularly to methods for improved corrosion resistance of Zircaloy-4 strip material (as opposed to other alloys or to Zircaloy-4 tubing).
In the development of nuclear reactors, such as pressurized water reactors and boiling water reactors, fuel designs impose significantly increased demands on all of the core strip and tubular cladding (strip is used for grids, guide tubes, and the like). The corrosion of strip is somewhat different from that of cladding as the two have quite different texture (strip is rolled, while cladding is pilgered). Such components are conventionally fabricated from the zirconium-based alloys, Zircaloy-2 and Zircaloy-4. Increased demands on such components will be in the form of longer required residence times and thinner structural members, both of which cause potential corrosion and/or hydriding problems.
Commercial reactors generally use either Zircaloy-2 or Zircaloy-4, (see U.S. Pat. Nos. 2,772,964 and 3,148,055). Zircaloy-2 is a zirconium alloy having about 1.2-1.7, weight percent (all percents herein are weight percent) tin, 0.07-0.20 percent iron, about 0.05-0.15 percent chromium, and about 0.03-0.08 percent nickel. Zircaloy-4 contains about 1.2-1.7 percent tin, about 0.18-0.24 percent iron, and about 0.07-0.13 percent chromium.
Fabrication schedules for Zircaloy-4 have been developed with regard to corrosion resistance. Generally, different processing methods result in either good uniform or good nodular corrosion resistance but not both. The effect of thermal treatment variations has been accounted for by the cumulative A-parameter (see Steinberg, et al. "Zirconium in the Nuclear Industry: Sixth International Symposium, ASTM STP 824, American Society for Testing and Materials, Philadelphia, 1984). Charquet, et al. (see D. Charquet, et al. "Influence of Variations in Early Fabrication Steps on Corrosion, Mechanical Properties and Structures of Zircaloy-4 Products", Zirconium in the Nuclear Industry Seventh International Symposium, ASTM, STP 939, ASTM, 1987, pp. 431-447) investigated the effects of early stage tube processing on uniform (400.degree. C.) and nodular (500.degree. C.) corrosion. Charquet's results showed that, with increasing cumulative A-parameter, nodular corrosion increases, but that uniform corrosion decreases.
SUMMARY OF THE INVENTION
This is an improved method of fabricating Zircaloy-4 strip. The method is of the type wherein Zircaloy-4 material is vacuum melted, forged, hot reduced, beta-annealed, quenched, hot rolled, subjected to a post-hot-roll anneal and then reduced by at least two cold rolling steps, including a final cold rolling to final size, with intermediate annealing between the cold rolling steps and with a final anneal after the last cold rolling step. The improvement comprises: (a) utilizing a maximum processing temperature of 620.degree. C. between the quenching and the final cold rolling to final size; (b) utilizing a maximum intermediate annealing temperature of 520.degree. C.; and (c) utilizing hot rolling, post-hot-roll annealing, intermediate annealing and final annealing time-temperature combinations to give an A parameter of between 4.times.10.sup.-19 and 7.times.10.sup.-18 hour, where segment parameters are calculated for the hot rolling step and each annealing step, the segment parameters are calculated by taking the time, in hours, for which that step is performed, to the (-40,000/T) power, in which T is the temperature, in degrees K, at which the step is performed, and where the A parameter is the sum of the segment parameters.
Preferably, the hot rolling and the post-hot-roll anneal are at 560.degree.-620.degree. C. and the intermediate annealing is at 400.degree.-520.degree. C. and the final anneal after the last cold rolling step is at 560.degree.-710.degree. C.
Preferably, the hot rolling and the post-hot-roll anneal are for 1.5-3 hours and the intermediate annealing is for 1.5-15 hours and the final anneal after the last cold rolling step is for 1-5 hours, and the beta-anneal is at 1015.degree.-1130.degree. C. for 2-30 minutes.